ES2965289T3 - Method to purify contaminated polymers - Google Patents

Abstract

A method for purifying a recovered polymer, such as a recovered polymer from post-consumer use or post-industrial use, is disclosed. The method involves obtaining the recovered polymer and contacting it at elevated temperature and pressure with a fluid solvent to produce an extracted recovered polymer. The extracted recovered polymer is dissolved in a solvent at an elevated temperature and pressure to produce a polymer solution, which is purified at an elevated temperature and pressure by contacting the polymer solution with a solid medium to produce a purer polymer solution. . A purer polymer is then separated from the purer polymer solution. (Automatic translation with Google Translate, without legal value)

Description

DESCRIPTION

Method to purify contaminated polymers

field of invention

The present invention generally relates to a method for purifying contaminated polymers through the use of a pressurized solvent and a solid medium. More specifically, this invention relates to a method for purifying recycled polymers, such as post-consumer and industrial recycled plastics, to produce a virgin-like, odorless, transparent and colorless polymer. It is especially useful for the purification of polyolefins, such as polyethylene and polypropylene.

Background of the invention

Polymers, especially synthetic plastics, are constantly present in everyday life due to their relatively low production costs and a good balance of material properties. Synthetic plastics are used in a wide variety of applications, such as packaging, automotive components, medical devices, and consumer goods. To meet the high demand for these applications, tens of billions of synthetic plastics are produced worldwide annually. The vast majority of synthetic plastics are produced from increasingly scarce fossil sources, such as oil and natural gas. Additionally, manufacturing synthetic plastics from fossil sources produces CO2 as a byproduct.

The continued use of synthetic plastics has therefore resulted in millions of tonnes of plastic waste being generated each year. Although the majority of plastic waste is managed through municipal solid waste programs, there is a significant portion of plastic waste in the environment in the form of litter, which has a visual impact and is potentially harmful to ecosystems. Plastic waste often ends up washed into river systems and, ultimately, into sea waters.

Plastic recycling has emerged as a solution to mitigate the problems associated with the systematic use of plastics. The recovery and reuse of plastics keeps waste out of landfills and reduces demand for virgin plastics made from fossil sources, thereby reducing greenhouse gas emissions. In developed regions, such as the United States and the European Union, plastic recycling is increasing due to increased awareness by consumers, businesses, and industrial manufacturing operations. Most recycled materials, including plastics, are mixed into a single stream that is collected and processed by a material recovery facility (MRF). At the MRF, materials are sorted, washed and packaged for resale. Plastics can be classified into individual materials, such as high-density polyethylene (HDPE) or poly(ethylene terephthalate) (PET), or mixed streams of other common plastics, such as polypropylene (PP), low-density density polyethylene (low density polyethylene - LDPE), poly(vinyl chloride) (PVC), polystyrene (PS), polycarbonate (PC) and polyamides (PA). The single or mixed streams can then be separated, washed and reprocessed to obtain a granule that is suitable for reuse in plastics processing, for example blow and injection molding.

Although recycled plastics are sorted into predominantly uniform streams and washed with aqueous and/or caustic solutions, the final reprocessed granule often remains highly contaminated with unwanted residual impurities, such as spoiled food residues and residual perfume components. Additionally, recycled plastic granules, except those from recycled beverage containers, have a dark color due to the mixture of dyes and pigments commonly used to color plastic items. Although there are some applications that are insensitive to color and contamination (for example, black plastic paint containers and hidden automotive components), most applications require uncolored granules. The need for high quality “virgin type” recycled resin is especially important for food and drug contact applications, such as food packaging. In addition to being contaminated with impurities and mixed dyes, many recycled resin products are often heterogeneous in chemical composition and may contain a significant amount of polymeric contamination, such as polyethylene (PE) contamination in recycled PP and vice versa.

Mechanical recycling, also known as secondary recycling, is the process of converting recycled plastic waste into a form that can be reused for further manufacturing. A more detailed examination of mechanical recycling and other plastic recovery processes is described in S.M. Al-Salem, P. Lettieri, J. Baeyens, “Recycling and recovery routes of plastic solid waste (PSW): A review”, Waste Management, volume 29, number 10, October 2009, pages 2625-2643, ISSN 0956- 053X. Although advances in mechanical recycling technology have improved the quality of recycled polymers to some extent, there are fundamental limitations of mechanical decontamination methods, such as the physical entrapment of pigments within a polymer matrix. Thus, even with improvements in mechanical recycling technology, the dark color and high levels of chemical contamination in currently available recycled plastic waste prevent wider use of recycled resins in the plastics industry.

To overcome the fundamental limitations of mechanical processes, many methods have been developed to purify contaminated polymers through chemical methods or chemical recycling. Most of these methods use solvents to decontaminate and purify the polymers. The use of solvents allows for the extraction of impurities and polymer solution, which also allows for alternative separation technologies.

For example, US Patent 7,935,736 describes a method for recycling polyester from polyester-containing waste using a solvent to dissolve the polyester before cleaning. US-7,935,736 also describes the need to use a precipitant to recover the polyester from the solvent.

In another example, a method for producing a polypropylene blend from a plastic blend comprising other polymers is described in US Patent 6,555,588. US-6,555,588 describes the extraction of contaminants from a polymer at a temperature below the solution temperature of the polymer in the selected solvent, such as hexane, for a specified residence period. Raising the temperature of the solvent (or a second solvent) to dissolve the polymer prior to filtration is further described in US Patent 6,555,588. US-6,555,588 also describes the use of shear or fluidity to precipitate polypropylene from solution. The polypropylene blend described in US-6,555,588 contained polyethylene contamination up to 5.6% by weight.

In another example, a process for obtaining purified polyolefins from a polyolefin-containing plastic mixture or a polyolefin-containing waste is described in European Patent Application No. 849,312 (translated from German to English). Patent application No. 849,312 describes the extraction of polyolefin mixtures or waste with a hydrocarbon fraction of gasoline or diesel fuel with a boiling point above 90 ° C at temperatures between 90 ° C and the boiling point of boiling of the hydrocarbon solvent. Patent Application No. 849,312 further describes contacting a hot polyolefin solution with bleaching clay and/or activated carbon to remove foreign components from the solution. Cooling the solution to temperatures below 70°C to crystallize the polyolefin and then removing the adhering solvent by heating the polyolefin above the melting point of the polyolefin is also described in Patent Application No. 849,312, or evaporating the adherent solvent in vacuo or passing a gas stream through the polyolefin precipitate, and/or extracting the solvent with an alcohol or acetone boiling below the melting point of the polyolefin.

In another example, US Patent 5,198,471 describes a method for separating polymers from a physically mixed solid mixture (e.g., plastic waste) containing a plurality of polymers using a solvent at a first lower temperature to form a first single phase solution and a remaining solid component. Heating the solvent to higher temperatures to dissolve additional polymers that do not dissolve at the first lower temperature is also described in US Patent 5,198,471. Patent US-5,198,471 describes the filtration of undissolved components.

In another example, US-5,223,021 describes a method for extracting pure polymer components from a multi-component structure (e.g., carpet waste) by dissolving each component at a suitable temperature and pressure in a supercritical fluid. and then varying the temperature and/or pressure to extract particulate components in a sequence. However, similar to US-5,198,471, US-5,223,021 only describes the filtration of the precipitated component.

In another example, US Patent 5,739,270 describes a method and apparatus for continuously separating a polymeric component of a plastic from contaminants and other components of the plastic using an auxiliary solvent (cosolvent) and a working fluid. The auxiliary solvent at least partially dissolves the polymer and the second fluid (which is in a liquid, critical or supercritical state) dissolves the polymer components and precipitates a portion of the dissolved polymer from the auxiliary solvent. US-5,739,270 further describes the step of filtering the thermoplastic auxiliary solvent (with or without the working fluid) to remove particulate contaminants, such as glass particles.

Known solvent-based methods for purifying contaminated polymers, as described above, do not produce any "virgin-type" polymers. In the above methods, co-dissolution and therefore cross-contamination of other polymers often occurs. If adsorbent is used, a filtration and/or centrifugation step is often employed to remove the used adsorbent from the solution. Additionally, isolation processes to remove solvent, such as heating, vacuum evaporation and/or precipitation with the use of a precipitation chemical, are used to produce a polymer free of residual solvent.

Therefore, there remains a need for an improved solvent-based method for purifying contaminated polymers with the use of a solvent that is easily and economically removed from the polymer, is relatively simple in terms of the number of unit operations, produces a polymer without a significant amount of polymer cross-contamination, produce an essentially colorless polymer, and produce an essentially odorless polymer.

US5554657 relates to a process for recirculating a mixed polymer recirculation stream containing polyester polymers, especially polyethylene terephthalate (PET) typically in the form of carbonated soft drink or other containers.

WO 98/51717 describes a process for deformulation of a polymer by solvent solution filtration that includes formulated polymers and/or polymer products in a recirculated stream. Formulated polymeric products include a certain amount of soluble polymers and/or insoluble polymers, colorants, formulations and soluble and/or insoluble additives.

Document EP 849312 refers to a process for the production of polyolefin free of impurities from plastic mixtures containing POL or waste materials (II), which comprises the extraction of (II) with a hydrocarbon fraction and, in If applicable, isolate the crystallized polyolefin.

DE 43 19 180 relates to a process for recycling used polystyrene (PS) articles comprising dissolving the PS in styrene monomer, purifying the solution, performing the polymerization in a conventional polymerization system and removing the residual solvent.

US-5,233,021 relates to a method for extracting pure components from a multi-component structure by dissolving each component at a suitable temperature and pressure in a supercritical fluid and then varying the temperature and/or pressure to extract components in the form of particles in a sequence.

WO 0194457 describes a process for recovering polyamide material from post-industrial and post-consumer products containing the polyamide material and insoluble materials.

EP 0759456 relates to a process for recycling carpet waste containing polyamide by extracting the polyamide from the carpet waste with an extraction agent containing an aliphatic alcohol, after which the polyamide is recovered from the extract.

Summary of the invention

A method for purifying regenerated polymers is described.

The method of the present invention is defined in claim 1.

Specifically, the method of the present invention is a method for purifying regenerated polymers, wherein the regenerated polymers are polyolefins, the method comprising:

to. Obtaining a regenerated polymer wherein the regenerated polymer is selected from the group consisting of post-consumer use polymers, post-industrial use polymers, and combinations thereof;

b. Contacting the regenerated polymer at a temperature of 80°C to 220°C and a pressure of 150 psig (1.03 MPa) to 15,000 psig (103.42 MPa) with a first fluid solvent to produce an extracted regenerated polymer, wherein the polymer is practically insoluble in the fluid solvent;

c. Dissolve the extracted regenerated polymer in a solvent from the group consisting of the first fluid solvent, a second fluid solvent, and mixtures thereof, at a temperature of 90°C to 220°C, and at a pressure of 350 psig (2, 41 MPa) to 20,000 psig (137.90 MPa) to produce a polymer solution, wherein the fluid solvents have a standard boiling point less than 70 °C;

d. Purifying said polymer solution at a temperature of 90 ° C to about 220 ° C and at a pressure of 350 psig (2.41 MPa) to 20,000 psig (137.90 MPa) by contacting said polymer solution with solid media to produce a purer polymer solution, wherein the solid media is selected from the group consisting of inorganic substances, carbon-based substances or mixtures thereof or wherein the solid media is recycled glass; and wherein the inorganic substances are selected from the group consisting of silicon oxides, aluminum oxides, iron oxides, aluminum silicates, magnesium silicates, amorphous volcanic glasses, silica, silica gel, diatomite, sand, quartz, glass regenerated, alumina, perlite, fuller's earth, bentonite and mixtures thereof, and the carbon-based substances are selected from the group consisting of anthracite coal, carbon black, coke, activated carbon, cellulose and mixtures thereof ; and

and. Separating a purer polymer from said purer polymer solution; wherein said second fluid solvent has the same chemical composition or a different chemical composition as the first fluid solvent.

In one embodiment, the purer polymer is separated from the purer polymer solution at a temperature of 0°C to about 220°C, and at a pressure of 0 psig (0 MPa) to 2,000 psig (13.79 MPa).

In one embodiment, the regenerated polymer is recycled post-consumer derived polymer. In another embodiment, the regenerated polymer is a polypropylene homopolymer or a primarily polypropylene copolymer. In another embodiment, the polymer is a polyethylene homopolymer or a primarily polyethylene copolymer.

In one embodiment, the fluid solvent has a standard boiling point of less than 0°C and greater than -45°C and a standard enthalpy change of vaporization of less than 25 kJ/mol. In another embodiment, the fluid solvent is selected from the group consisting of olefinic hydrocarbons, aliphatic hydrocarbons and mixtures thereof. In one embodiment, the aliphatic hydrocarbon is selected from the group consisting of C<1>-C<6>aliphatic hydrocarbons and mixtures thereof. In another embodiment, the aliphatic hydrocarbons and mixtures thereof comprise primarily C<4> aliphatic hydrocarbons.

In one embodiment, the fluid solvent consists essentially of C<4> liquefied petroleum gas. In another embodiment, the fluid solvent is n-butane, butane isomers, or mixtures thereof.

In one embodiment, the temperature in the extraction, dissolution and purification steps is 110°C to 170°C. In one embodiment, the pressure in the contact stage is 1,100 psig (7.58 MPa) to 5,500 psig (37.92 MPa).

In one embodiment, the pressure in the contact stage is less than 1,100 psig (7.58 MPa).

In one embodiment, the pressure in the dissolution stage is greater than 1,100 psig (7.58 MPa). In another embodiment, the pressure in the dissolution stage is greater than 5,500 psig (37.92 MPa). The solid medium is selected from the group consisting of inorganic substances, carbon-based substances or mixtures thereof or wherein the solid medium is recycled glass. Inorganic substances are selected from the group consisting of silicon oxides, aluminum oxides, iron oxides, aluminum silicates, magnesium silicates, amorphous volcanic glasses, silica, silica gel, diatomite, sand, quartz, regenerated glass, alumina , perlite, fuller's earth, bentonite and mixtures thereof, and the carbon-based substances are selected from the group consisting of anthracite coal, carbon black, coke, activated carbon, cellulose and mixtures thereof.

In another embodiment, the contact of the polymer solution with the solid medium is carried out in a compacted bed of the solid medium. In one embodiment, the compacted bed has a length greater than 20 cm.

Brief description of the drawings

Fig. 1 is a block flow diagram showing the main steps of an embodiment of the present invention. Fig. 2 is a calibration curve for the calculation of polyethylene content in polypropylene using enthalpy values from DSC measurements.

Fig. 3 is a diagram of the experimental apparatus used in the examples.

Fig. 4 is a photograph of the illustrative polypropylene specimens.

Fig. 5 is a bar graph of the opacity and odor intensity of several examples of polypropylene.

Fig. 6 is a photograph of the illustrative polyethylene test tubes.

Fig. 7 is a bar graph of the opacity and odor intensity of the polyethylene examples.

Detailed description of the invention

I. Definitions

As used herein, the term “recycled polymer” refers to a polymer used for a previous purpose and then recovered for further processing.

As used herein, the term “post-consumer” refers to a source of material that originates after the end consumer has used the material in a product or consumer item. As used herein, the term “post-consumer recycle” refers to a material that is produced after the end consumer has used the material and deposited the material into a waste stream. As used herein, the term “post-industrial use” refers to a source of a material that originates during the manufacturing of a product or article.

As used herein, the term “fluid solvent” refers to a substance that can exist in a liquid state under specific conditions of temperature and pressure. In some embodiments, the fluid solvent may be a predominantly homogeneous chemical composition of one molecule or isomer, while in other embodiments the fluid solvent may be a mixture of several different molecular compositions or isomers. Furthermore, in some embodiments of the present invention, the term “fluid solvent” may be applied to substances that are at, near or above the critical temperature and critical pressure (critical point) of said substance. It is well known to those skilled in the art that substances above the critical point of that substance are known as “supercritical fluids” which do not have the typical physical properties (i.e., density) of a liquid.

As used herein, the term “dissolved” refers to the at least partial incorporation of a solute (polymeric or non-polymeric) into a solvent at the molecular level. Furthermore, the thermodynamic stability of the solute/solvent solution can be described by the following Equation 1:

where AGmx is the variation in Gibbs free energy corresponding to the mixing of a solute with a solvent, AHmix is the variation in mixing enthalpy, Tes is the absolute temperature, and ASmx is the mixing entropy. To maintain a stable solution of a solute in a solvent, the Gibbs free energy must be negative and minimal. Therefore, any combination of solute and solvent that minimizes a negative Gibbs free energy at suitable temperatures and pressures can be used for the present invention.

As used herein, the term “standard boiling point” refers to the boiling temperature at an absolute pressure of exactly 100 kPa (1 bar, 14.5 psi, 0.9869 atm), as established by the International Union of Pure and Applied Chemistry (IUPAC).

As used herein, the term “standard enthalpy change of vaporization” refers to the enthalpy change necessary to transform a specified amount of a substance from a liquid to a vapor at the standard boiling point of the substance.

As used herein, the term “polymer solution” refers to a solution of a polymer dissolved in a solvent. The polymer solution may contain undissolved matter and therefore the polymer solution may also be a "suspension" of undissolved matter suspended in a polymer solution dissolved in a solvent.

As used herein, the term “solid medium” refers to a substance that exists in a solid state under the conditions of use. The solid medium can be crystalline, semicrystalline or amorphous. The solid medium can be granulated and can be supplied in different forms (i.e. spheres, cylinders, granules, etc.). If the solid medium is granular, the particle size and particle size distribution of the solid medium may be defined by the mesh size used to classify the granular medium. An example of standard mesh size designations can be found in the American Standard ASTM E11 “Standard Specification for Woven Wire Test Sieve Cloth and Test Sieves.” Society for Testing and Materials (ASTM). The solid medium may also be a nonwoven fibrous mat or a woven fabric.

As used herein, the term “purer polymer solution” refers to a polymer solution that has fewer contaminants than the same polymer solution before a purification step.

As used herein, the term “virgin type” means essentially free of contaminants, free of pigments, free of odors, homogeneous and of properties similar to virgin polymers.

As used herein, the term “primarily polypropylene copolymer” refers to a copolymer with more than 70 mol% repeating units of propylene.

As used herein, the term “primarily polyethylene copolymer” refers to a copolymer with more than 70 mole % ethylene repeating units.

II. Method to purify contaminated polymers

Surprisingly, it has been discovered that certain fluid solvents, which in a preferred embodiment exhibit temperature- and pressure-dependent polymer solubility, when used in a relatively simple process, can be used to purify contaminated polymers, especially recovered or recycled polymers. , to a quality similar to a virgin one. This process, illustrated in Fig. 1, comprises 1) obtaining a regenerated polymer (Step a in Fig. 1), followed by 2) extracting the polymer with a fluid solvent at an extraction temperature (T<e>) and at an extraction pressure (P<e>) (Step b in Fig. 1), followed by 3) the dissolution of the polymer in a fluid solvent at a dissolution temperature (T<d>) and at a dissolution pressure (P <d>) (Stage c in Fig. 1), followed by 4) bringing the dissolved polymer solution into contact with solid media at a dissolution temperature (T<d>) and a dissolution pressure (P< d>) (Step d in Fig. 1), followed by separation of the polymer from the fluid solvent (Step e in Fig. 1). In one embodiment of the present invention, the purified polymers, which may be derived from post-consumer waste streams, are substantially free of contaminants, free of pigments, free of odor, are homogeneous and have properties similar to raw polymers.

Furthermore, in a preferred embodiment, the physical properties of the fluid solvent of the present invention may allow for more energy efficient methods of separating the fluid solvent from the purified polymer.

regenerated polymer

The method for purifying regenerated polymers includes obtaining a regenerated polymer. For the purposes of the present invention, the regenerated polymer comes from post-consumer, post-industrial, post-commercial, and/or other special waste streams. For example, post-consumer polymer waste can arise from curbside recycling streams, where end consumers place used polymers from packaging and products into a designated container for collection by a waste hauler or recycler. Post-consumer polymeric waste can also result from “return” to the establishment programs in which the consumer brings the polymeric waste to a establishment and places the polymeric waste in an identified collection container. An example of post-industrial polymeric waste may be polymeric waste produced during the manufacturing or shipping of a product or item that has been collected as unusable material by the manufacturer (i.e. scraps, materials that do not meet technical requirements, waste commissioning). An example of polymeric waste from a special waste stream may be polymeric waste derived from the recycling of electronic waste, also known as electronic scrap ("e-waste"). Another example of special polymers from a special waste stream may be polymeric waste derived from automobile recycling. Another example of polymeric waste from a special waste stream may be polymeric waste derived from the recycling of used carpets/rugs and fabrics.

For the purposes of the present invention, the regenerated polymer is a homogeneous composition of a single polymer or a mixture of several different polymer compositions. Suitable regenerated polymer compositions are homopolymers and copolymers of polyolefins, such as polyethylene and isotactic polypropylene, polyolefins.

The regenerated polymer may also contain various pigments, dyes, processing aids, stabilizing additives, fillers and other performance additives added to the polymer during polymerization or conversion of the original polymer to the final form of an article. Non-limiting examples of pigments are organic pigments, such as copper phthalocyanine, inorganic pigments, such as titanium dioxide, and other pigments that may be apparent to those skilled in the art. A non-limiting example of an organic dye is Basic Yellow 51. Non-limiting examples of processing aids are antistatic agents, such as glycerol monostearate, and slip promoting agents, such as erucamide. A non-limiting example of a stabilizing additive is octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate. Non-limiting examples of fillers are calcium carbonate, talc and glass fibers.

Solvent

The fluid solvent of the present invention has a standard boiling point of less than about 70°C. Pressurization maintains the solvents, which have standard boiling points below the operating temperature range of the present invention, in a state in which there is little or no solvent vapor. In one embodiment, the fluid solvent with a standard boiling point of less than about 70°C is selected from the group consisting of carbon dioxide, ketones, alcohols, ethers, esters, alkenes, alkanes, and mixtures thereof. Non-limiting examples of fluid solvents with standard boiling points less than about 70°C are carbon dioxide, acetone, methanol, dimethyl ether, diethyl ether, ethylmethyl ether, tetrahydrofuran, methyl acetate, ethylene, propylene, 1-butene, 2-butene, isobutylene, 1-pentene, 2-pentene, branched isomers of pentene, 1-hexene, 2-hexene, methane, ethane, propane, n-butane, isobutane, n-pentane, isopentane, neopentane, n-hexane , isohexane isomers and other substances that may be apparent to those skilled in the art.

The selection of the appropriate solvent or solvent mixture will depend on which regenerated polymer or polymer mixture is being purified by the present invention. Furthermore, the selection of the polymer being purified and the corresponding fluid solvent used will depend on the temperature and pressure ranges used to carry out the steps of the present invention. A summarized study of the behavior of the polymer phase in solvents of the type described in the present invention is provided in the following reference: McHugh et al. (1999)Chem. Rev.99:565-602.

Extraction

The method of purifying regenerated polymers includes contacting a regenerated polymer with a fluid solvent at a temperature and pressure at which the polymer is essentially insoluble in the fluid solvent. Without wishing to be bound by theory, applicants believe that the temperature and pressure-dependent solubility can be controlled to prevent the fluid solvent from completely dissolving the polymer; however, the fluid solvent can diffuse into the polymer and draw out any extractable contamination. Removable contamination can be residual processing aids added to the polymer, residual product formulations that come into contact with the polymer, such as perfumes and flavorings, dyes, and any other extractable materials that have been intentionally added or accidentally incorporated into the polymer. polymer, for example, during waste collection and subsequent accumulation with other waste materials.

In one embodiment, controlled extraction can be achieved by setting the temperature of the polymer/fluid solvent system and then controlling the pressure below a pressure or range of pressures, where the polymer dissolves in the fluid solvent. In another embodiment, controlled extraction is achieved by setting the pressure of the polymer/solvent system and then controlling the temperature below a temperature or temperature range where the polymer dissolves in the fluid solvent. In temperature and pressure controlled extraction of the polymer with a fluid solvent a suitable pressure vessel is used and may be configured in a manner that allows continuous extraction of the polymer with the fluid solvent. In one embodiment of the present invention, the pressure vessel may be a continuous liquid-liquid extraction column where the molten polymer is pumped at one end of the extraction column and the fluid solvent is pumped at the same end or at the end. opposite of the extraction column. In another embodiment, the fluid containing the extracted contamination is removed from the process. In another embodiment, the fluid containing the extracted contamination is purified, recovered and recycled for use in the extraction step or in a different step of the process. In one embodiment of the present invention, the extraction can be carried out as a batch method, where the regenerated polymer is fixed in a pressure vessel and the fluid solvent is pumped continuously through the fixed polymer phase. The extraction time or amount of fluid solvent used will depend on the desired purity of the final purest polymer and the amount of extractable contamination in the starting regenerated polymer. In another embodiment, the fluid containing the extracted contamination is contacted with solid medium in a separate step as described below in the "Purification" section. In another embodiment, a method for purifying regenerated polymers includes contacting a regenerated polymer with a fluid solvent at a temperature and pressure at which the polymer is molten and in a liquid state. In another embodiment, the regenerated polymer is contacted with the fluid solvent at a temperature and pressure at which the polymer is in a solid state.

In one embodiment, a method of purifying regenerated polymers includes contacting polyethylene with a fluid solvent at a temperature and pressure at which the polyethylene remains substantially undissolved. In another embodiment, a method for purifying the regenerated polymers includes contacting polyethylene with n-butane at a temperature of about 80°C to about 220°C. In another embodiment, a method for purifying the regenerated polymers includes contacting polyethylene with n-butane at a temperature of about 100°C to about 200°C. In another embodiment, a method for purifying the regenerated polymers includes contacting polyethylene with n-butane at a temperature of about 130°C to about 180°C. In another embodiment, a method of purifying the regenerated polymers includes contacting polyethylene with n-butane at a pressure of about 150 psig (1.03 MPa) to about 6,500 psig (44.82 MPa). In another embodiment, a method of purifying the regenerated polymers includes contacting polyethylene with n-butane at a pressure of about 3,000 psig (20.68 MPa) to about 6,000 psig (41.37 MPa). In another embodiment, a method of purifying the regenerated polymers includes contacting polyethylene with n-butane at a pressure of about 4,500 psig (31.03 MPa) to about 5,500 psig (37.92 MPa).

In another embodiment, a method of purifying the regenerated polymers includes contacting polyethylene with propane at a temperature of about 80°C to about 220°C. In another embodiment, a method of purifying the regenerated polymers includes contacting polyethylene with propane at a temperature of about 100°C to about 200°C. In another embodiment, a method of purifying the regenerated polymers includes contacting polyethylene with propane at a temperature of about 130°C to about 180°C. In another embodiment, a method of purifying the regenerated polymers includes contacting polyethylene with propane at a pressure of about 1,000 psig (6.89 MPa) to about 15,000 psig (103.42 MPa). In another embodiment, a method of purifying the regenerated polymers includes contacting polyethylene with propane at a pressure of about 2,000 psig (13.79 MPa) to about 10,000 psig (68.95 MPa). In another embodiment, a method of purifying the regenerated polymers includes contacting polyethylene with n-butane at a pressure of about 5,000 psig (34.47 MPa) to about 9,000 psig (62.05 MPa).

In one embodiment, a method of purifying regenerated polymers includes contacting polypropylene with a fluid solvent at a temperature and pressure at which the polypropylene remains essentially undissolved. In another embodiment, a method of purifying the regenerated polymers includes contacting polypropylene with n-butane at a temperature of about 80°C to about 220°C. In another embodiment, a method of purifying the regenerated polymers includes contacting polypropylene with n-butane at a temperature of about 100°C to about 200°C. In another embodiment, a method of purifying the regenerated polymers includes contacting polypropylene with n-butane at a temperature of about 130°C to about 180°C. In another embodiment, a method of purifying the regenerated polymers includes contacting polypropylene with n-butane at a pressure of about 150 psig (1.03 MPa) to about 3,000 psig (20.68 MPa). In another embodiment, a method of purifying the regenerated polymers includes contacting polypropylene with n-butane at a pressure of about 1,000 psig (6.89 MPa) to about 2,750 psig (18.96 MPa). In another embodiment, a method of purifying the regenerated polymers includes contacting polypropylene with n-butane at a pressure of about 1,500 psig (10.34 MPa) to about 2,500 psig (17.24 MPa).

In another embodiment, a method of purifying the regenerated polymers includes contacting polypropylene with propane at a temperature of about 80°C to about 220°C. In another embodiment, a method of purifying the regenerated polymers includes contacting polypropylene with propane at a temperature of about 100°C to about 200°C. In another embodiment, a method of purifying the regenerated polymers includes contacting polypropylene with propane at a temperature of about 130°C to about 180°C. In another embodiment, a method of purifying the regenerated polymers includes contacting polypropylene with propane at a pressure of about 200 psig (1.38 MPa) to about 8,000 psig (55.16 MPa). In another embodiment, a method of purifying the regenerated polymers includes contacting polypropylene with propane at a pressure of about 1,000 psig (6.89 MPa) to about 6,000 psig (41.37 MPa). In another embodiment, a method of purifying the regenerated polymers includes contacting polypropylene with propane at a pressure of about 2,000 psig (13.79 MPa) to about 4,000 psig (27.58 MPa).

Dissolution

The method of purifying the regenerated polymers includes dissolving the regenerated polymer in a fluid solvent at a temperature and pressure at which the polymer dissolves in the fluid solvent. Without wishing to impose any theory, the applicants believe that the temperature and pressure can be controlled so that thermodynamically favorable dissolution of the recovered polymer in a fluid solvent is possible. Furthermore, the temperature and pressure can be controlled so that dissolution of a particular polymer or polymer mixture is possible without dissolving other polymers or polymer mixtures at the same time. This controllable dissolution allows the separation of polymers from polymer blends.

In one embodiment of the present invention, a method of purifying regenerated polymers includes dissolving the contaminated regenerated polymers in a solvent that does not dissolve the contaminants under the same temperature and pressure conditions. Contaminants can include pigments, fillers, dirt and other polymers. These contaminants are released from the regenerated polymer upon dissolution and are then removed from the polymer solution by a subsequent solid-liquid separation step.

In one embodiment of the present invention, a method of purifying the regenerated polymers includes dissolving polyethylene in a fluid solvent at a temperature and pressure at which the polyethylene dissolves in the fluid solvent. In another embodiment, a method of purifying the regenerated polymers includes dissolving polyethylene in n-butane at a temperature of about 90°C to about 220°C. In another embodiment, a method of purifying the regenerated polymers includes dissolving polyethylene in n-butane at a temperature of about 100°C to about 200°C. In another embodiment, a method for purifying the regenerated polymers includes dissolving polyethylene in n-butane at a temperature of about 130°C to about 180°C. In another embodiment, a method of purifying the regenerated polymers includes dissolving polyethylene in n-butane at a pressure of about 1,000 psig (6.89 MPa) to about 12,000 psig (82.74 MPa). In another embodiment, a method of purifying the regenerated polymers includes dissolving polyethylene in n-butane at a pressure of about 2,000 psig (13.79 MPa) to about 10,000 psig (68.95 MPa). In another embodiment, a method of purifying the regenerated polymers includes dissolving polyethylene in n-butane at a pressure of about 4,000 psig (27.58 MPa) to about 6,000 psig (41.37 MPa).

In another embodiment, a method of purifying the regenerated polymers includes dissolving polyethylene in propane at a temperature of about 90°C to about 220°C. In another embodiment, a method of purifying the regenerated polymers includes dissolving polyethylene in propane at a temperature of about 100°C to about 200°C. In another embodiment, a method of purifying the regenerated polymers includes dissolving polyethylene in propane at a temperature of about 130°C to about 180°C. In another embodiment, a method of purifying the regenerated polymers includes dissolving polyethylene in propane at a pressure of about 3,000 psig (20.68 MPa) to about 20,000 psig (137.90 MPa). In another embodiment, a method of purifying the regenerated polymers includes dissolving polyethylene in propane at a pressure of about 5,000 psig (34.47 MPa) to about 15,000 psig (103.42 MPa). In another embodiment, a method of purifying the regenerated polymers includes dissolving polyethylene in propane at a pressure of about 8,000 psig (55.16 MPa) to about 11,000 psig (75.84 MPa).

In one embodiment, a method of purifying the regenerated polymers includes dissolving polypropylene in a fluid solvent at a temperature and pressure at which the polypropylene dissolves in the fluid solvent. In another embodiment, a method of purifying the regenerated polymers includes dissolving polypropylene in n-butane at a temperature of about 90°C to about 220°C. In another embodiment, a method of purifying the regenerated polymers includes dissolving polypropylene in n-butane at a temperature of about 100°C to about 200°C. In another embodiment, a method for purifying the regenerated polymers includes dissolving polypropylene in n-butane at a temperature of about 130°C to about 180°C. In another embodiment, a method of purifying the regenerated polymers includes dissolving polypropylene in n-butane at a pressure of about 350 psig (2.41 MPa) to about 4,000 psig (27.57 MPa). In another embodiment, a method of purifying the regenerated polymers includes dissolving polypropylene in n-butane at a pressure of about 1,000 psig (6.89 MPa) to about 3,500 psig (24.13 MPa). In another embodiment, a method of purifying the regenerated polymers includes dissolving polypropylene in nbutane at a pressure of about 2,000 psig (13.79 MPa) to about 3,000 psig (20.68 MPa).

In another embodiment, a method of purifying the regenerated polymers includes dissolving polypropylene in propane at a temperature of about 90°C to about 220°C. In another embodiment, a method of purifying the regenerated polymers includes dissolving polypropylene in propane at a temperature of about 100°C to about 200°C. In another embodiment, a method of purifying the regenerated polymers includes dissolving polypropylene in propane at a temperature of about 130°C to about 180°C. In another embodiment, a method of purifying the regenerated polymers includes dissolving polypropylene in propane at a pressure of about 2,000 psig (13.79 MPa) to about 8,000 psig (55.16 MPa). In another embodiment, a method of purifying the regenerated polymers includes dissolving polypropylene in propane at a pressure of about 3,000 psig (20.68 MPa) to about 6,000 psig (41.37 MPa). In another embodiment, a method of purifying the regenerated polymers includes dissolving polypropylene in propane at a pressure of about 3,500 psig (24.13 MPa) to about 5,000 psig (34.47 MPa).

Purification

The method of purifying regenerated polymers includes contacting a contaminated polymer solution with solid media at a temperature and pressure at which the polymer remains dissolved in the fluid solvent. The solid medium of the present invention is any solid material that removes at least part of the contamination from a solution of regenerated polymer dissolved in the fluid solvent of the present invention. Although not intended to impose any theory, the applicants believe that the solid medium eliminates contamination through various mechanisms. Non-limiting examples of possible mechanisms include adsorption, absorption, size exclusion, ion exclusion, ion exchange, and other mechanisms that may be apparent to those skilled in the art. Furthermore, pigments and other contaminants commonly present in regenerated polymers may be polar compounds and may preferably interact with the solid medium, which may also be at least slightly polar. Polar-polar interactions are especially favorable when non-polar solvents, such as alkanes, are used as the fluid solvent. The solid medium is selected from the group consisting of inorganic substances, carbon-based substances, or mixtures thereof, or wherein the solid medium is recycled glass. Inorganic substances are selected from the group consisting of silicon oxides, aluminum oxides, iron oxides, aluminum silicates, magnesium silicates, amorphous volcanic glasses, silica, silica gel, diatomite, sand, quartz, regenerated glass, alumina , perlite, fuller's earth, bentonite and mixtures thereof, and the carbon-based substances are selected from the group consisting of anthracite coal, carbon black, coke, activated carbon, cellulose and mixtures thereof.

In one embodiment of the present invention, the solid medium is contacted with the polymer in a container for a specific amount of time while the solid medium is stirred. In another embodiment, the solid medium is removed from the purer polymer solution by a solid-liquid separation step. Non-limiting examples of solid-liquid separation steps include filtration, decantation, centrifugation and precipitation. In another embodiment of the present invention, the contaminated polymer solution is passed through a fixed bed of solid medium. In another embodiment of the present invention, the height or length of the stationary bed of the solid medium is greater than 5 cm. In another embodiment of the present invention, the height or length of the stationary bed of the solid medium is greater than 10 cm. In another embodiment of the present invention, the height or length of the stationary bed of the solid medium is greater than 20 cm. In another embodiment of the present invention, the solid medium is replaced as necessary to maintain the desired purity of the polymer. In another embodiment, the solid medium is regenerated and reused in the purification step. In another embodiment, the solid medium is regenerated by fluidizing the solid medium during a backwash step.

In one embodiment, a method of purifying regenerated polyethylene includes contacting a polyethylene/fluid solvent solution with solid media at a temperature and pressure where the polyethylene remains dissolved in the fluid solvent. In another embodiment, a method for purifying regenerated polymers includes contacting a polyethylene/n-butane solution with solid media at a temperature of about 90°C to about 220°C. In another embodiment, a method for purifying regenerated polymers includes contacting a polyethylene/n-butane solution with solid media at a temperature of about 100°C to about 200°C. In another embodiment, a method for purifying regenerated polymers includes contacting a polyethylene/n-butane solution with solid media at a temperature of about 130°C to about 180°C. In another embodiment, a method of purifying the regenerated polymers includes contacting a polyethylene/n-butane solution with solid media at a pressure of about 1,000 psig (6.89 MPa) to about 12,000 psig (82.74 MPa). In another embodiment, a method of purifying the regenerated polymers includes contacting a polyethylene/n-butane solution with solid media at a pressure of about 2,000 psig (13.79 MPa) to about 10,000 psig (68.95 MPa). In another embodiment, a method of purifying the regenerated polymers includes contacting a polyethylene/n-butane solution with solid media at a pressure of about 4,000 psig (27.58 MPa) to about 6,000 psig (41.37 MPa).

In another embodiment, a method of purifying regenerated polymers includes contacting a polyethylene/propane solution with solid media at a temperature of about 90°C to about 220°C. In another embodiment, a method for purifying regenerated polymers includes contacting a polyethylene/propane solution with solid media at a temperature of about 100°C to about 200°C. In another embodiment, a method for purifying regenerated polymers includes contacting a polyethylene/propane solution with solid media at a temperature of about 130°C to about 180°C. In another embodiment, a method for purifying regenerated polymers includes contacting a polyethylene/propane solution with solid media at a pressure of about 3,000 psig (20.68 MPa) to about 20,000 psig (137.90 MPa). In another embodiment, a method of purifying regenerated polymers includes contacting a polyethylene/propane solution with solid media at a pressure of about 5,000 psig (34.47 MPa) to about 15,000 psig (103.42 MPa). In another embodiment, a method of purifying regenerated polymers includes contacting a polyethylene/propane solution with solid media at a pressure of about 8,000 psig (55.16 MPa) to about 11,000 psig (75.84 MPa).

In one embodiment, a method for purifying recovered polypropylene includes contacting a polypropylene/fluid solvent solution with solid medium at a temperature and pressure at which the polypropylene remains dissolved in the fluid solvent. In another embodiment, a method for purifying regenerated polymers includes contacting a polypropylene/n-butane solution with solid media at a temperature of about 90°C to about 220°C. In another embodiment, a method for purifying regenerated polymers includes contacting a polypropylene/n-butane solution with solid media at a temperature of about 100°C to about 200°C. In another embodiment, a method for purifying regenerated polymers includes contacting a polypropylene/n-butane solution with solid media at a temperature of about 130°C to about 180°C. In another embodiment, a method of purifying the regenerated polymers includes contacting a polypropylene/n-butane solution with solid media at a pressure of about 350 psig (2.41 MPa) to about 4,000 psig (27.57 MPa). In another embodiment, a method of purifying the regenerated polymers includes contacting a polypropylene/n-butane solution with solid media at a pressure of about 1,000 psig (6.89 MPa) to about 3,500 psig (24.13 MPa). In another embodiment, a method for purifying regenerated polymers includes contacting a polypropylene/n-butane solution with solid media at a pressure of about 2,000 psig (13.79 MPa) to about 3,000 psig (20.68 MPa).

In another embodiment, a method for purifying regenerated polymers includes contacting a polypropylene/propane solution with solid media at a temperature of about 90°C to about 220°C. In another embodiment, a method for purifying regenerated polymers includes contacting a polypropylene/propane solution with solid media at a temperature of about 100°C to about 200°C. In another embodiment, a method for purifying regenerated polymers includes contacting a polypropylene/propane solution with solid media at a temperature of about 130°C to about 180°C. In another embodiment, a method for purifying regenerated polymers includes contacting a polypropylene/propane solution with solid media at a pressure of about 2,000 psig (13.79 MPa) to about 8,000 psig (55.16 MPa). In another embodiment, a method of purifying regenerated polymers includes contacting a polypropylene/propane solution with solid media at a pressure of about 3,000 psig (20.68 MPa) to about 6,000 psig (41.37 MPa). In another embodiment, a method for purifying regenerated polymers includes contacting a polypropylene/propane solution with solid media at a pressure of about 3,500 psig (24.13 MPa) to about 5,000 psig (34.47 MPa).

Separation

The method of purifying the regenerated polymers includes separating the purer polymer from the fluid solvent at a temperature and pressure at which the polymer precipitates from solution and no longer dissolves in the fluid solvent. In another embodiment, precipitation of the purer polymer from the fluid solvent is achieved by reducing the pressure at a fixed temperature. In another embodiment, precipitation of the purer polymer from the fluid solvent is achieved by reducing the temperature to a fixed pressure. In another embodiment, precipitation of the purer polymer from the fluid solvent is achieved by increasing the temperature at a fixed pressure. In another embodiment, precipitation of the purer polymer from the fluid solvent is achieved by reducing both temperature and pressure. The solvent can be passed partially or completely from the liquid phase to the vapor phase by controlling the temperature and pressure. In another embodiment, the precipitated polymer is separated from the fluid solvent without completely converting the fluid solvent to a 100% vapor phase by controlling the temperature and pressure of the solvent during the separation step. Separation of the precipitated purer polymer is achieved by any liquid-liquid or liquid-solid separation method. Non-limiting examples of liquid-liquid or liquid-solid separations include filtration, decantation, centrifugation and precipitation.

In one embodiment, a method for purifying regenerated polyethylene includes separating the polyethylene from a polyethylene/fluid solvent solution at a temperature and pressure where the polyethylene is precipitated from the solution. In another embodiment, a method for purifying the regenerated polymers includes separating the polyethylene from a polyethylene/n-butane solution at a temperature of about 0°C to about 220°C. In another embodiment, a method of purifying the regenerated polymers includes separating the polyethylene from a polyethylene/nbutane solution at a temperature of about 50°C to about 175°C. In another embodiment, a method for purifying the regenerated polymers includes separating the polyethylene from a polyethylene/n-butane solution at a temperature of about 100°C to about 160°C. In another embodiment, a method of purifying the regenerated polymers includes separating the polyethylene from a polyethylene/n-butane solution at a pressure of about 0 psig (0 MPa) to about 4,000 psig (27.58 MPa). In another embodiment, a method of purifying the regenerated polymers includes separating the polyethylene from a polyethylene/n-butane solution at a pressure of about 50 psig (0.34 MPa) to about 2,000 psig (13.79 MPa). In another embodiment, a method of purifying the regenerated polymers includes separating the polyethylene from a polyethylene/n-butane solution at a pressure of about 75 psig (0.52 MPa) to about 1,000 psig (6.89 MPa).

In another embodiment, a method of purifying the regenerated polymers includes separating the polyethylene from a polyethylene/propane solution at a temperature of about -42°C to about 220°C. In another embodiment, a method of purifying the regenerated polymers includes separating the polyethylene from a polyethylene/propane solution at a temperature of about 0°C to about 150°C. In another embodiment, a method of purifying the regenerated polymers includes separating the polyethylene from a polyethylene/propane solution at a temperature of about 50°C to about 130°C. In another embodiment, a method of purifying the regenerated polymers includes separating the polyethylene from a polyethylene/propane solution at a pressure of about 0 psig (0 MPa) to about 15,000 psig (103.42 MPa). In another embodiment, a method of purifying the regenerated polymers includes separating the polyethylene from a polyethylene/propane solution at a pressure of about 50 psig (0.34 MPa) to about 5,000 psig (34.47 MPa). In another embodiment, a method of purifying the regenerated polymers includes separating the polyethylene from a polyethylene/propane solution at a pressure of about 75 psig (0.52 MPa) to about 1,000 psig (6.89 MPa).

In one embodiment, a method of purifying the regenerated polymers includes separating the polypropylene from a polypropylene/fluid solvent solution at a temperature and pressure at which the polypropylene precipitates from the solution. In another embodiment, a method for purifying the regenerated polymers includes separating the polypropylene from a polypropylene/n-butane solution at a temperature of about 0°C to about 220°C. In another embodiment, a method for purifying the regenerated polymers includes separating the polypropylene from a polypropylene/nbutane solution at a temperature of about 100°C to about 200°C. In another embodiment, a method for purifying the regenerated polymers includes separating the polypropylene from a polypropylene/n-butane solution at a temperature of about 130°C to about 180°C. In another embodiment, a method of purifying the regenerated polymers includes separating the polypropylene from a polypropylene/n-butane solution at a pressure of about 0 psig (0 MPa) to about 2,000 psig (13.79 MPa). In another embodiment, a method of purifying the regenerated polymers includes separating the polypropylene from a polypropylene/n-butane solution at a pressure of about 50 psig (0.34 MPa) to about 1,500 psig (10.34 MPa). In another embodiment, a method of purifying the regenerated polymers includes separating the polypropylene from a polypropylene/nbutane solution at a pressure of about 75 psig (0.52 MPa) to about 1,000 psig (6.89 MPa).

In another embodiment, a method of purifying regenerated polymers includes separating polypropylene from a polypropylene/propane solution at a temperature of about -42°C to about 220°C. In another embodiment, a method for purifying regenerated polymers includes separating polypropylene from a polypropylene/propane solution at a temperature of about 0°C to about 150°C. In another embodiment, a method for purifying regenerated polymers includes separating polypropylene from a polypropylene/propane solution at a temperature of about 50°C to about 130°C. In another embodiment, a method of purifying the regenerated polymers includes separating polypropylene from a polypropylene/propane solution at a pressure of about 0 psig (0 MPa) to about 6,000 psig (41.37 MPa). In another embodiment, a method of purifying the regenerated polymers includes separating the polypropylene from a polypropylene/propane solution at a pressure of about 50 psig (0.34 MPa) to about 3,000 psig (20.68 MPa). In another embodiment, a method of purifying the regenerated polymers includes separating the polypropylene from a polypropylene/propane solution at a pressure of about 75 psig (0.52 MPa) to about 1,000 psig (6.89 MPa).

III Test method

The test methods described in the present invention are used to measure the effectiveness of various methods for purifying polymers. Specifically, the methods described demonstrate the effectiveness of a given purification method by improving color and translucency/clarity (i.e., making the color and opacity of the regenerated polymer more similar to that of a colorless virgin polymer), reducing o eliminate elemental contamination (i.e., remove heavy metals), reduce or eliminate contamination by non-combustible matter (i.e., inorganic fillers), reduce or eliminate volatile compounds (especially volatile compounds that contribute to the bad odor of regenerated polymers ) and reduce or eliminate polymeric contamination (i.e., polyethylene contamination in polypropylene).

Color and opacity measurement:

The color and opacity/translucency of a polymer are important parameters that determine whether or not a polymer can achieve the desired visual aesthetics of an item made from the polymer. Regenerated polymers, especially regenerated polymers obtained after consumption, are typically dark in color and opaque due to residual pigments, fillers, and other contamination. Therefore, color and opacity measurements are important parameters in determining the effectiveness of a method for purifying polymers.

Before color measurement, samples of polymer powders or granules were compression molded into square test specimens measuring 30 mm wide x 30 mm long x 1 mm thick (with rounded corners). The powder samples were first densified at room temperature (approx. 20-23 °C) by cold pressing the powder to obtain a sheet using clean, unused aluminum foil as a non-stick contact layer between stainless steel plates. Then, approximately 0.85 g of cold-pressed powder or granules were compressed into test specimens in a previously heated Carver Press model C (Carver, Inc., Wabash, N 46992-0554, USA). at 200 °C using aluminum plates, unused non-stick layers of aluminum foil and a stainless steel filler with a cavity corresponding to the aforementioned dimensions of the square test specimens. The samples were heated for 5 minutes before pressure was applied. After 5 minutes, the press was then compressed with at least 2 tons (1.81 metric tons) of hydraulic pressure for at least 5 seconds and then the pressure was released. The molding stack was then removed and placed between two thick flat metal heat sinks to cool it. The aluminum foil non-stick contact layers were then peeled off the sample and discarded. Excess material accumulated around the sample on at least one face was stripped toward the molding edge and the sample was then pressed through the mold. Each test specimen was visually evaluated for the presence of voids/bubble defects and only samples without defects in the color measurement area (0.7 in. (17.78 mm) minimum diameter) were used for measurement. of the color.

The color of each sample was characterized using the International Commission on Illumination (CIE) three-dimensional color space L*, a*, b*. The dimensionL* is a measure of the clarity of a sample, corresponding L*=0 to the darkest black sample and L*=100 to the brightest white sample. The a* dimension is a measure of the red or green color of a sample, with positive values of a* corresponding to a red color and negative values of a* to a green color. The b* dimension is a measure of the blue or yellow color of a sample, with positive b* values corresponding to a blue color and negative b* values corresponding to a yellow color. The L*a*b*values of each 30 mm wide x 30 mm long x 1 mm thick square test specimen sample were measured on a HunterLab model LabScan XE spectrophotometer (Hunter Associates Laboratory, Inc., Reston, VA 20190-5280, USA). The spectrophotometer was configured with D65 as the standard illuminant, an observer angle of 10°, a view area diameter of 1.75 in. (44.45 mm), and a hole diameter of 0.7 in. (17.78mm).

The opacity of each sample, which is a measure of the amount of light passing through the sample (i.e., a measure of the translucency of the sample), was determined using the previously mentioned HunterLab spectrophotometer using the opacity mode of contrast index. Two measurements were made to determine the opacity of each sample. One to measure the gloss value of the sample that had a white support, Ywhite support, and one to measure the gloss value of the sample that had a black support, Yblack support. The opacity was then calculated from the gloss values using the following equation 2:

(II)

%Opacity = } support black) *100

*(s o p o r t e b la n c o<)>

Elemental analysis:

Many regenerated polymers have excessively high concentrations of heavy metal contamination. The presence of heavy metals, for example, lead, mercury, cadmium, and chromium, may prevent the use of recovered polymers in certain applications, such as food or drug contact applications or medical device applications. Therefore, measuring the concentration of heavy metals is important in determining the effectiveness of a method to purify polymers.

Element analysis was performed by Inductively Coupled Plasma Mass Spectrometry (ICP-MS). Test solutions at n = 2 to n = 6 were prepared depending on sample availability by combining ~0.25 g of sample with 4 mL of concentrated nitric acid and 1 mL of concentrated hydrofluoric acid (HF). Samples were digested using an Ultrawave microwave digestion protocol that consisted of a 20-min ramp at 125°C, a 10-min ramp at 250°C, and holding for 20 min at 250°C. The digested samples were cooled to room temperature. The digested samples were diluted to 50 ml after adding 0.25 ml of Ge and 100 ppm Rh as internal standard. To evaluate the measurement accuracy, pre-digestion spikes prepared by addition of virgin polymer were prepared. The virgin polymer spiked samples were weighed using the same procedure mentioned above and the appropriate amount of each standard element of interest was added, which included the following: Na, Al, Ca, Ti, Cr, Fe, Ni, Cu, Zn, Cd and Pb. The additions were prepared at two different levels: a “low level addition” and a “high level addition”. Each spike was prepared in triplicate. In addition to adding virgin polymer, a blank was also added to verify that no errors had occurred during pipetting and to track recovery during the process. The blank spiked samples were also prepared in triplicate at the two different levels and treated in the same manner as the spiked virgin polymer and test samples. A 9-point calibration curve was fabricated by preparing 0.05, 0.1, 0.5, 1, 5, 10, 50, 100, and 500 ppb solutions containing Na, Al, Ca, Ti, Cr, Fe, Ni, Cu, Zn, Cd and Pb. All calibration standards were prepared by diluting pure reference standard solutions and 0.25 mL of 100 ppm Ge and Rh as internal standard with 4 mL of concentrated nitric acid and 1 mL of concentrated hF. Prepared standards, test samples, and spiked test samples were analyzed using an Agilent 8800 ICP-QQQMS, optimized according to the manufacturer's recommendations. The m/z value monitored for each analyte and the collision cell gas used for the analysis were as follows: Na, 23 m/z, H2; Al, 27 m/z, H2; Ca, 40 m/z, H2; Ti, 48 m/z, H2; Cr, 52 m/z, He; Fe, 56 m/z, H2; Ni, 60 m/z; without gas; Cu, 65 m/z, without gas; Zn, 64 m/z, He; Cd, 112 m/z; H2; Pb, sum of 206 > 206, 207 > 207, 208 > 208 m/z, no gas; Ge, 72 m/z, all modes; Rh, 103 m/z, all modes. Ge was used as internal standard for all elements < 103 m/z and Rh was used for all elements > 103 m/z.

Residual ash content:

Many regenerated polymers contain various fillers, for example calcium carbonate, talc and glass fiber. Although useful in the original regenerated polymer application, these fillers alter the physical properties of a polymer in a way that may be undesirable for the next application of the regenerated polymer. Therefore, measuring the amount of charge is important when determining the effectiveness of a method for purifying polymers. Thermogravimetric analysis (TGA) was carried out to quantify the amount of non-combustible materials in the sample (sometimes called ash content). Approximately 5–15 mg of sample was loaded into a platinum sample cuvette and heated to 700 °C at a rate of 20 °C/min in an air atmosphere on a TA Instruments model Q500 TGA instrument. The sample was kept isothermal for 10 min at 700 °C. The percentage of residual mass was measured at 700 °C after isothermal holding. Smell analysis:

Odor sensory analysis was performed by placing approximately 3 g of each sample in a 20 mL glass vial and equilibrating the sample at room temperature for at least 30 min. After equilibration, each vial was opened and a grader trained to determine odor intensity and descriptor profile sniffed the headspace. The intensity of the odor was rated according to the following scale:

5 = Very strong

4 = Strong

3 = Moderate

2 = Weak to moderate

1 = Weak

0 = No smell

Polymer contamination analysis:

Many regenerated polymers, especially regenerated polymers originating from mixed stream sources, may contain undesirable polymer contamination. Without wishing to be bound by theory, polymer contamination, for example, polyethylene contamination in polypropylene, can affect the physical properties of the polymer due to the presence of heterogeneous phases and the resulting weak interconnections. Additionally, polymer contamination can also increase the opacity of the polymer and influence the color. Therefore, measurement of polymer contamination is important when determining the effectiveness of a method for purifying polymers.

Semi-crystalline polymer contamination was assessed using Differential Scanning Calorimetry (DSC). For example, to measure the amount of polyethylene contamination in polypropylene, a set of five polypropylene/polyethylene blends was prepared with 2, 4, 6, 8 and 10 wt% Formolene® HB5502F HDPE (Formosa Plastics Corporation, USA). USA) in polypropylene Pro-fax 6331 (LyondellBasell Industries Holdings, B.V.). Approximately 5-15 mg of each sample was sealed in an aluminum DSC tray and analyzed on a TA Instruments model Q2000 with the following method:

1. Equilibrate at 30.00 °C

2. Ramp 20.00 °C/min to 200.00 °C

3. End mark of cycle 0

4. Ramp 20.00 °C/min to 30.00 °C

5. End mark of cycle 1

6. Ramp 20.00 °C/min to 200.00 °C

7. End mark of cycle 2

8. Ramp 20.00 °C/min to 30.00 °C

9. End mark of cycle 3

10. Ramp 5.00 °C/min to 200.00 °C

11. End mark of cycle 4

The enthalpy of fusion for the HDPE peak around 128 °C was calculated for each sample of known HDPE content using the 5.00 °C/min DSC thermogram. A linear calibration curve, shown in Fig. 2, was established, plotting the enthalpy of fusion versus the known HDPE concentration (wt %).

Samples having unknown PE content were analyzed using the same DSC equipment and method mentioned above. The PE content was calculated using the aforementioned calibration curve. The specific HDPE used to generate the calibration curve will most likely have a different degree of crystallinity than the polyethylene (or polyethylene blend) contamination that may be present in a regenerated polymer sample. The degree of crystallinity can independently influence the enthalpy of fusion measured for polyethylene and therefore influence the resulting calculation of polyethylene content. However, the DSC test method described herein is for use as a relative measurement to compare the effectiveness of different methods for purifying polymers and should not be considered a rigorous quantification of the polyethylene content in a polymer blend. Although the aforementioned method describes the measurement of polyethylene contamination in polypropylene, this method can be applied to the measurement of other semicrystalline polymers using different temperature ranges and peaks in the DSC thermogram. Additionally, alternative methods, such as nuclear magnetic resonance (NMR) spectroscopy, can also be used to measure the amount of both semicrystalline and amorphous polymeric contamination in a sample.

Examples

The following examples describe and demonstrate embodiments within the scope of the present invention in more detail. The examples are presented for illustrative purposes only and are not intended as limitations of the present invention, since many variations thereof are possible without departing from the spirit and scope of the invention.

Example 1

A sample of color flakes mixed with recycled polypropylene obtained after consumption from a recycled resin supplier was obtained. The post-consumer recycled polypropylene was from the United States and Canada. The mixed color flake, as received, was homogenized by blending in a Century/W&P ZSK30 twin screw extruder equipped with 30 mm general purpose screws, each with standard mixing and transport elements. The screw rotation speed was approximately 50 rpm, the feeder output was approximately 20 lb/hour (9.07 kg/hour), and the cylinder temperature ranged from approximately 210°C in the die to approximately 150°. C in the feed throat. The gray strand coming out of the extruder was cooled in a water bath at room temperature, dried with air and cut to obtain pearls.

The sample was characterized using the test method described herein and the resulting data is summarized in Table 1. The purpose of this example is to show the properties of a representative post-consumer recycled resin before purification.

The tablets and the corresponding square test specimens were dark gray as indicated by the L*a*b* values of the square test specimens. The opacity of the samples averaged approximately 100% opacity (i.e., no translucency). A photograph of the square test specimen is shown in Fig. 4 as Example 1. As shown in Fig. 4, the specimen was dark in color and lacked translucency.

This example serves as a representative basis of heavy metal contamination present in recycled polypropylene obtained post-consumer. Compared to other examples, heavy metal contamination was found to be much higher in post-consumer recycled polypropylene.

The samples of Example 1 had ash content values averaging approximately 1.2117 wt%, which also serves as a basis for the amount of non-combustible substances often present in post-consumer recycled polypropylene.

This example serves as a representative basis of contamination by odorous compounds present in recycled polypropylene obtained after consumption. The samples from Example 1 were found to have an odor intensity of 3.75 on a 5-point scale (5 being the highest intensity), and were described as having a “garbage,” “dusty,” or “ acre.”

This example serves as a representative basis of polyethylene contamination present in recycled polypropylene obtained post-consumer. The samples of Example 1 had polyethylene contents averaged at approximately 5.5% by weight.

Example 2

The post-consumer recycled polypropylene mixed color flake sample described in Example 1 was processed using the experimental apparatus shown in Fig. 3 and the following procedure: 1. 237 g of mixed color flakes were loaded into the pressurized vessel of a 1.1 L extraction column with an internal diameter (ID) of 1.75" (4.45 cm) and a length of 28" (71.12 cm) that was heated to a surface temperature external 175°C.

2. The liquid n-butane solvent was pressurized to approximately 2,150 psig (14.82 MPa) using a positive displacement pump and preheated to a temperature of approximately 110 °C using two heat exchangers before being introduced into the bottom of the extraction column.

3. The fluid stream leaving the top of the extraction column was introduced into the top of a second 0.5 L pressure vessel with an ID of 2" (5.08 cm) and a length of approximately 8.5” (21.59 cm) which was heated to an external surface temperature of 175 °C. The second pressurized container contained 150 ml of silica gel (Silicycle Ultra Pure Silica Gels, SiliaFlash GE60, Parc-Technologies, EE. . or U.) previously mixed in a beaker with 150 ml of aluminum oxide (Activated Alumina, Selexsorb CDX, 7x14, BASF, USA).

4. The fluid stream exiting the bottom of the second pressure vessel was depressurized through an expansion valve into a side-arm Erlenmeyer flask. After depressurizing the fluid stream into the Erlenmeyer flask, the solvent vapor was purged through the side arm opening hole and the liquids/solids were collected in the flask. The n-butane solvent was eluted through the system at 2,150 psig (14.82 MPa) until no additional material was observed accumulating in the flask. 19.93 g of white solids were collected and marked as 'Fraction 1'.

5. The Erlenmeyer flask was replaced with a clean, empty flask, and then the system pressure was increased to 2,400 psig (16.55 MPa).

6. The system pressure was maintained at 2,400 psig (16.55 MPa) until no other solid material was observed eluting from the system. 89.35 g of white solids were collected and marked as 'Fraction 2'.

7. The Erlenmeyer flask was replaced with a clean, empty flask, and then the system pressure was increased to 2,500 psig (17.24 MPa).

8. The system pressure was maintained at 2,500 psig (17.24 MPa) until no other solid material was observed eluting from the system. 58.18 g of white solids were collected and marked as 'Fraction 3'.

9. The Erlenmeyer flask was replaced with a clean, empty flask, and then the system pressure was increased to 2,600 psig (17.93 MPa).

10. The system pressure was maintained at 2,600 psig (17.93 MPa) until no other solid material was observed eluting from the system. 7.29 g of white solids were collected and marked as 'Fraction 4'.

11. The Erlenmeyer flask was replaced with a clean, empty flask, and then the system pressure was increased to 3,000 psig (20.68 MPa).

12. The system pressure was maintained at 3,000 psig (20.68 MPa) until no other solid material was observed eluting from the system. 5.58 g of whitish solids were collected and marked as 'Fraction 5'. 13. Samples collected in each flask were allowed to degas at room temperature and pressure for at least two days before being characterized using the test methods described herein. Data for the white solid material collected at 2,400 psig (16.55 MPa) as Fraction 2 is summarized in Table 1. Table 1. Color, Contamination and Odor Removal from Examples 1-4

Table 2. Removal of color, contamination and odor from Examples 5-8

_____ _____ _____ _____ _____ _____ _____ _____

The solids isolated in fractions 1-5 of this example were white. When the white solids of fraction 2 were compression molded into square test specimens, the specimens were colorless and transparent and had an appearance similar to virgin polypropylene. A photograph of the square test specimen is shown in Fig. 4 as Example 2. As shown in Fig. 4, the specimen was clear and comparable in terms of color and translucency to virgin polypropylene. The L*a*b*values showed that the square test specimens were essentially colorless and showed a very significant improvement in terms of color over the square test specimens of Example 1 (i.e., polypropylene obtained post-consumption such and how it was received). The L*values for the square test specimens of fraction 2 of Example 2 had an average of 85.29, much better compared to the L*values of the square test specimens of Example 1, which had an average of 39.76. . The opacity of the square test specimens of fraction 2 of Example 2, which had an average opacity of 7.90% (i.e., a translucency of approximately 92%), was also greatly improved compared to the opacity values of the square test specimens of Example 1, which had an average opacity of 100%.

The concentration of heavy metal contamination for the samples of fraction 2 of Example 2 was also much better compared to the samples of Example 1. For example, the concentration of sodium in the samples of fraction 2 of Example 2 had an average of only 2,630 ppb while the sodium concentration in the samples of Example 1 averaged 136,000 ppb (a reduction of approximately 98%). The concentrations of aluminum, iron, cadmium, and lead were below the limit of quantification for the fraction 2 samples of Example 2, while the concentration of the same elements in the samples of Example 1 averaged 192,000, 108,000, 1,620, and 12,166. ppb, respectively. All concentrations of all other elements measured (calcium, titanium, chromium, nickel, copper and zinc) were reduced by more than 99% for the fraction 2 samples of Example 2 relative to the samples of Example 1.

The samples of fraction 2 of Example 2 had an average ash content value of approximately 0.2897% by weight, which was significantly lower than the ash content values corresponding to the samples of Example 1, which had an average of approximately 1.2117% by weight.

The samples of fraction 2 of Example 2 were found to have an odor intensity of 0.5 on a 5-point scale (5 being the most intense), which was much better compared to the odor intensity of the samples of the Example 1, which had an odor intensity of 3.75. Although they had a low odor intensity, the samples of fraction 2 of Example 2 have been described as having a “plastic” or “gasoline” type odor samples similar to that of virgin polypropylene.

Any polyethylene content in the samples from fraction 2 of Example 2 was below the limit of quantitation, which was greatly improved compared to the polyethylene content of the samples from Example 1, which averaged approximately 5.5% by weight.

Fig. 5 is a bar graph of the opacity and odor intensity of the purified recycled polypropylene of Example 2 compared to the untreated recycled polypropylene (Example 1), the recycled polypropylene treated according to the method described in EP0849312 A1 ( Example 8) and a comparative sample of virgin polypropylene. As shown in Fig. 5, the purified recycled polypropylene of Example 2 had both low opacity and low odor intensity and was similar to the comparative virgin polypropylene sample.

Example 3

The post-consumer recycled polypropylene mixed color flake sample described in Example 1 was processed using the experimental apparatus shown in Fig. 3 and the following procedure:

1. 225 g of mixed color flakes were loaded into the pressurized vessel of a 1.1 L extraction column with an inner diameter (ID) of 1.75" (44.45 mm) and a length of 28" ( 71.12 cm) that was heated to an external surface temperature of 135 °C.

2. The liquid n-butane solvent was pressurized to approximately 1,000 psig (6.89 MPa) using a positive displacement pump and preheated to a temperature of approximately 90 °C using two heat exchangers before being introduced into the bottom of the extraction column.

3. The fluid stream leaving the top of the extraction column was introduced into the top of a second 0.5 L pressure vessel with an ID of 2" (5.08 cm) and a length of approximately 8.5" (21.59 cm) that was heated to an external surface temperature of 135°C. The second pressurized container contained 150 ml of silica gel (Silicycle Ultra Pure Silica Gels, SiliaFlash GE60, Parc-Technologies, USA) previously mixed in a beaker with 150 ml of aluminum oxide (Activated Alumina, Selexsorb CDX , 7x14, BASF, USA).

4. The fluid stream exiting the bottom of the second pressure vessel was depressurized through an expansion valve into a side-arm Erlenmeyer flask. After depressurizing the fluid stream into the Erlenmeyer flask, the solvent vapor was purged through the side arm opening hole and the liquids/solids were collected in the flask. The n-butane solvent was eluted through the system at 1,000 psig (6.89 MPa) until no additional material was observed accumulating in the flask. 27.52 g of whitish solids were collected and marked as 'Fraction 1'.

5. The Erlenmeyer flask was replaced with a clean, empty flask, and then the system pressure was increased to 1,500 psig (10.34 MPa).

6. The system pressure was maintained at 1,500 psig (10.34 MPa) until no other solid material was observed eluting from the system. 59.25 g of whitish solids were collected and marked as 'Fraction 2'.

7. The fraction 2 sample collected at 1,500 psig (10.34 MPa) was then allowed to degas at room temperature and pressure for at least two days before being characterized using the test methods described herein.

Data for the fraction 2 sample collected at 1,500 psig (10.34 MPa) are summarized in Table 1.

The solids isolated in fraction 2 in this example were slightly off-white in color. When these solids were compression molded into square test specimens, the fraction 2 specimens were almost colorless and transparent and had an appearance almost similar to that of virgin polypropylene. A photograph of the square test specimen is shown in Fig. 4 as Example 3. As shown in Fig. 4, the specimen was clear and comparable in terms of color and translucency to virgin polypropylene. The L*a*b*values also showed that the square test specimens of fraction 2 were essentially colorless and showed a very significant improvement in terms of color with respect to the square test specimens of Example 1 (i.e., polypropylene obtained from post-consumer form as received). The L*values for the square test specimens of fraction 2 of Example 3 had an average of 84.57, much better compared to the L*values of the square test specimens of Example 1, which had an average of 39.76 . The opacity of the square test specimens of fraction 2 of Example 3, which had an average opacity of 9.58% (i.e., a translucency of approximately 90%), was also greatly improved compared to the opacity values of the square test specimens of Example 1, which had an average opacity of 100%.

The concentration of heavy metal contamination for the samples of fraction 2 of Example 3 was also much better compared to the samples of Example 1. For example, the sodium concentrations in the samples of fraction 2 of Example 3 had an average of 36,100 ppb while the sodium concentrations in the samples from Example 1 averaged 136,000 ppb (a reduction of approximately 74%). The concentrations of iron, cadmium, and lead were below the limit of quantification for the fraction 2 samples of Example 3, while the concentrations of the same elements in the samples of Example 1 averaged 108,000, 1,620, and 12,166 ppb, respectively. The concentrations of calcium, titanium, chromium, nickel, copper and zinc were reduced by more than 95% for the samples of fraction 2 of Example 3 relative to the samples of Example 1. The concentration of aluminum was reduced by approximately 74%. % in the same comparison.

The samples of fraction 2 of Example 3 had an average ash content value of approximately 0.1614% by weight, which was significantly lower than the ash content values corresponding to the samples of Example 1, which had an average of approximately 1.2117% by weight.

The samples of fraction 2 of Example 3 were found to have an odor intensity of 3 on a 5-point scale (5 being the most intense), which was somewhat better compared to the odor intensity of the samples of Example 1 , which had an odor intensity of 3.75. Samples from fraction 2 of Example 3 had an odor described as “plastic-like” or “solvent-like.”

Any polyethylene content in the samples from fraction 2 of Example 3 was below the limit of quantification, which was greatly improved compared to the polyethylene content of the samples from Example 1, which averaged approximately 5.5% by weight.

Example 4

The post-consumer recycled polypropylene mixed color flake sample described in Example 1 was processed using the experimental apparatus shown in Fig. 3 and the following procedure:

1. 236 g of mixed color flakes were loaded into the pressurized vessel of a 1.1 L extraction column with an internal diameter (ID) of 1.75" (44.45 mm) and a length of 28" ( 71.12 cm) that was heated to an external surface temperature of 175 °C.

2. The liquid hexanes (isomer mixture) solvent was pressurized to approximately 200 psig (1.38 MPa) using a positive displacement pump and preheated to a temperature of approximately 110 °C using two heat exchangers before being introduced into the bottom of the extraction column.

3. The fluid stream leaving the top of the extraction column was introduced into the top of a second 0.5 L pressure vessel with an ID of 2" (50.8 mm) and a length of approximately 8.5” (21.59 cm) which was heated to an external surface temperature of 175 °C. The second pressurized container contained 150 ml of silica gel (Silicycle Ultra Pure Silica Gels, SiliaFlash GE60, Parc-Technologies, EE. . or U.) previously mixed in a beaker with 150 ml of aluminum oxide (Activated Alumina, Selexsorb CDX, 7x14, BASF, USA).

4. The fluid stream exiting the bottom of the second pressure vessel was depressurized through an expansion valve into a side-arm Erlenmeyer flask. After depressurizing the fluid stream in the Erlenmeyer flask, the liquid/solid solution was collected in the flask. The hexanes solvent was eluted through the system at 200 psig (1.38 MPa) until no additional material was observed accumulating in the flask. 102.11 g of off-white solids (after evaporation of the solvent) were collected and marked as “Fraction 1”.

5. The Erlenmeyer flask was replaced with a clean, empty flask, and then the system pressure was increased to 300 psig (2.07 MPa).

6. The system pressure was maintained at 300 psig (2.07 MPa) until no other solid material was observed eluting from the system. 71.08 g of off-white solids were collected (after evaporation of the solvent) and marked as “Fraction 2”.

7. The hexanes solvent was removed from all samples by evaporation and then the samples were allowed to degas at room temperature and pressure for at least two days before being characterized using the test methods described herein.

Data for the fraction 1 sample collected at 200 psig (1.38 MPa) are summarized in Table 1.

The solids isolated in fraction 1 of this example were slightly off-white in color. When these solids from fraction 1 were compression molded into square test specimens, the specimens were almost colorless but their appearance was somewhat cloudy. A photograph of the square test specimen is shown in Fig. 4 as Example 4. As shown in Fig. 4, the specimen had improved color and opacity over Example 1, however, the specimen also had a Cloudy appearance compared to virgin PP. The L*a*b*values showed that the square test specimens of fraction 1 were essentially colorless and showed an improvement in terms of color with respect to the square test specimens of Example 1 (i.e., polypropylene obtained after consumption as received). The L*values for the square test specimens of fraction 1 of Example 4 had an average of 82.18, much better compared to the L*values of the square test specimens of Example 1, which had an average of 39.76 . The opacity of the square test specimens of fraction 1 of Example 4, which had an average opacity of 22.18%, also improved compared to the opacity values of the square test specimens of Example 1, which had an average 100% opacity. However, the opacity values for the square test specimens of fraction 1 of Example 4 did not improve as much as the opacity values for the square test specimens of fraction 2 of Examples 2 and 3. The contamination concentration of heavy metals for the fraction 1 samples of Example 4 was also much better compared to the samples of Example 1. For example, the sodium concentration in the fraction 1 samples of Example 4 averaged 2,790 ppb while The sodium concentration in the samples of Example 1 averaged 136,000 ppb (a reduction of approximately 97%). The concentrations of aluminum, calcium, titanium, chromium, iron, nickel, copper, zinc, cadmium and lead were reduced by more than 96% for the samples of fraction 1 of Example 4 with respect to the samples of Example 1.

The samples of fraction 1 of Example 4 had an average ash content value of approximately 0.2812% by weight, which was significantly lower than the ash content values corresponding to the samples of Example 1, which had an average of approximately 1.2117% by weight. The samples of fraction 1 of Example 4 were found to have an odor intensity of 2.25 on a 5-point scale (5 being the most intense), which was better compared to the odor intensity of the samples of Example 1, which had an odor intensity of 3.75. Although lower in intensity, samples from fraction 1 of Example 4 had an odor described as “minty,” “acidic,” “plastic,” and “burning.”

The samples of fraction 1 of Example 4 had average polyethylene content values of approximately 1.9% by weight, which improved compared to the polyethylene content of the samples of Example 1, which had an average of approximately 5.5 % in weigh.

Example 5

The post-consumer recycled polypropylene mixed color flake sample described in Example 1 was processed using the experimental apparatus shown in Fig. 3 and the following procedure: 1. 233 g of mixed color flakes were loaded into the pressurized vessel of a 1.1 L extraction column with an internal diameter (ID) of 1.75" (44.45 mm) and a length of 28" (71.12 cm) that was heated to a surface temperature external 175°C.

2. The liquid n-butane solvent was pressurized to approximately 2,050 psig (14.13 MPa) using a positive displacement pump and preheated to a temperature of approximately 110 °C using two heat exchangers before being introduced into the bottom of the extraction column.

3. The fluid stream leaving the top of the extraction column was introduced into the top of a second 0.5 L pressure vessel with an ID of 2" (50.8 mm) and a length of approximately 8.5” (21.59 cm) which was heated to an external surface temperature of 175 °C. The second pressure vessel contained 180 ml of silica gel (Silicycle Ultra Pure Silica gels, SiliaFlash GE60, Parc-Technologies, 4. The fluid stream exiting the bottom of the second pressure vessel was depressurized through an expansion valve into a side-arm Erlenmeyer flask. The solvent vapor was purged through the side arm opening hole and the liquids/solids were collected in the flask. The n-butane solvent was eluted through the system at 2,050 psig (14.13 MPa) until no more. Additional material accumulated in the flask was observed. 12.87 g of white solids were collected and were marked as 'Fraction 1'.

5. The Erlenmeyer flask was replaced with a clean, empty flask, and then the system pressure was increased to 2,500 psig (17.24 MPa).

6. The system pressure was maintained at 2,500 psig (17.24 MPa) until no other solid material was observed eluting from the system. 162.43 g of white solids were collected and marked as 'Fraction 2'. 7. The sample collected at 2,500 psig (17.24 MPa) was then allowed to degas at room temperature and pressure for at least two days before being characterized using the test methods described herein.

Data for the fraction 2 sample collected at 2,500 psig (17.24 MPa) are summarized in Table 2.

The solids isolated from fraction 2 in this example were white to slightly off-white in color. When these solids from fraction 2 were compression molded into square test specimens, the specimens were almost colorless but their appearance was somewhat cloudy. A photograph of the square test specimen is shown in Fig. 4 as Example 5. As shown in Fig. 4, the specimen had an improved appearance compared to Example 1, but was slightly cloudy when compared to the Virgin PP. The L*a*b*values showed that the square test specimens were essentially colorless and showed a very significant improvement in terms of color with respect to the square test specimens of Example 1 (i.e., polypropylene obtained after consumption as and how it was received). The L*values for the square test specimens of fraction 2 of Example 5 averaged 82.00, much better compared to the L*values of the square test specimens of Example 1, which averaged 39.76. . The opacity of the square test specimens of fraction 2 of Example 5, which had an average opacity of approximately 18.63%, was also improved compared to the opacity values of the square test specimens of Example 1, which had an average opacity of approximately 18.63%. average opacity of 100%. However, the opacity values for the square test specimens of fraction 2 of Example 5 did not improve as much as the opacity values for the square test specimens of fraction 2 of Examples 2 and 3. Although without intending to impose theory Some, the applicants believe that the improved, but still cloudy, appearance is due to the lower silica gel loading (i.e., shorter bed length) that allowed more contaminants to remain in the collected polymer.

The concentration of heavy metal contamination for the samples of fraction 2 of Example 5 was also much better compared to the samples of Example 1. For example, the concentration of sodium in the samples of fraction 2 of Example 5 had an average of 2,960 ppb while the sodium concentration in the samples of Example 1 averaged 136,000 ppb (a reduction of approximately 98%). Iron concentrations in samples from fraction 2 of Example 5 were below the limit of quantification while iron concentrations in samples from Example 1 averaged 108,000. The concentrations of aluminum, calcium, titanium, chromium, nickel, copper, zinc, cadmium and lead were reduced by more than 97% for the samples of fraction 2 of Example 5 with respect to the samples of Example 1.

The samples of fraction 2 of Example 5 had an average ash content value of approximately 0.5723% by weight, which was lower than the ash content values corresponding to the samples of Example 1, which had an average of approximately 1.2117% by weight.

The samples of fraction 2 of Example 5 were found to have an odor intensity of 4 on a 5-point scale (5 being the most intense), which was slightly higher compared to the odor intensity of the samples of Example 1 , which had an odor intensity of 3.75. Samples of fraction 2 of Example 5 had an odor described as “dirty”, “oily”, and “minty”. Although not intended to impose any theory, the applicants believe that the higher odor intensity of the samples of Example 5 was a result of the absorption of odorant molecules in silica gel during the first extraction step (i.e., the collection of fraction 1 ). Due to the smaller amount of silica gel (and therefore shorter bed height) used in Example 5, the absorbed odorant molecules likely eluted with the solids collected as fraction 2.

The samples of fraction 2 of Example 5 had an average polyethylene content value of approximately 1.7% by weight, which improved compared to the polyethylene content of the samples of Example 1, which had an average of approximately 5 .5% by weight.

Example 6

The samples of Example 6 were produced by combining the white solids of fraction 1 produced at 1,000 psig (6.89 MPa) from Example 3 with the white solids of fraction 2 produced at 1,500 psig (10.34 MPa) of Example 3. The combined sample of fraction 1 and fraction 2 was produced to demonstrate the performance of a method to purify polypropylene without the step of removing any extractable contamination. The data for fractions 1 and 2 of Example 3 combined are summarized in Table 2.

When the solids of this example were compression molded into square test specimens, the specimens had a similar appearance to the square test specimens of fraction 2 of Example 3. A photograph of the square test specimen is shown in Fig. .4 as Example 6. As shown in Fig. 4, the specimen was clear and comparable in terms of color and translucency to virgin polypropylene. The L*a*b*values showed that the square test specimens were essentially colorless and showed a very significant improvement in terms of color with respect to the square test specimens of Example 1 (i.e., polypropylene obtained after consumption as and how it was received). The L*values for the square test specimens of Example 6 averaged 84.51, much better compared to the L*values of the square test specimens of Example 1, which averaged 39.76. The opacity of the square test specimens of Example 6, which had an average opacity of 9.14% (i.e., a translucency of almost 91%), was also greatly improved compared to the opacity values of the test specimens of test squares of Comparative Example 1, which had an average opacity of 100%. The L*a*b* values and opacities of the square test specimens from Example 6 were also similar to the L*a*b* values and opacities of the square test specimens from fraction 2 of Example 3.

Analogously to fraction 2 of Example 3, the concentration of heavy metal contamination in the samples of Example 6 was also greatly improved compared to the samples of Example 1. For example, the concentration of sodium in the samples of Example 6 had an average of 19,700 ppb while the sodium concentration in the samples of Example 1 averaged 136,000 ppb (a reduction of approximately 86%). The concentrations of aluminum, calcium, titanium, chromium, iron, nickel, copper, zinc, cadmium and lead were reduced by more than 82% for the samples of Example 6 relative to the samples of Example 1.

The samples of Example 6 had average ash content values of approximately 0.4951% by weight, which was lower than the average ash content values for the samples of Example 1, of approximately 1.2117% by weight. Compared to the ash content values for the samples of fraction 2 of Example 3, the ash content values for the samples of Example 6 were slightly higher.

The samples of Example 6 were found to have an odor intensity of 3.75 on a 5-point scale (5 being the most intense), which was similar to the odor intensity of the samples of Example 1, which had an intensity smell of 3.75 too. The samples from Example 6 had an odor described as “chlorine-like,” “plastic-like,” “oily,” and “greasy.” Compared to the samples of fraction 2 of Example 3, the samples of Example 6 had a more intense odor.

Analogous to fraction 2 of Example 3, any polyethylene content in the samples of Example 6 was below the limit of quantification, which was greatly improved compared to the polyethylene content of the samples of Example 1, which averaged approximately 5. 5% by weight.

Example 7

The purpose of this example was to demonstrate the inferior performance of a method for purifying polypropylene without the step of contacting a polymer solution with solid media. The post-consumer recycled polypropylene mixed color flake sample described in Example 1 was processed using the experimental apparatus shown in Fig. 3 and the following procedure:

1. 231 g of mixed color flakes were loaded into the pressurized vessel of a 1.1 L extraction column with an inner diameter (ID) of 1.75" (44.45 mm) and a length of 28" ( 71.12 cm) that was heated to an external surface temperature of 175 °C.

2. The liquid n-butane solvent was pressurized to approximately 2,000 psig (13.79 MPa) using a positive displacement pump and preheated to a temperature of approximately 110 °C using two heat exchangers before being introduced into the bottom of the extraction column.

3. The fluid stream leaving the top of the extraction column was introduced into the top of a second 0.5 L pressure vessel with an ID of 2" (50.8 mm) and a length of approximately 8.5" (21.59 cm) that was heated to an external surface temperature of 175°C. The second pressure vessel did not contain any solid media in this example.

4. The fluid stream exiting the bottom of the second pressure vessel was depressurized through an expansion valve into a side-arm Erlenmeyer flask. After depressurizing the fluid stream into the Erlenmeyer flask, the solvent vapor was purged through the side arm opening hole and the liquids/solids were collected in the flask. The n-butane solvent was eluted through the system at 2,000 psig (13.79 MPa) until no additional material was observed accumulating in the flask. 20.82 g of cream colored solids were collected and marked as 'Fraction 1'.

5. The Erlenmeyer flask was replaced with a clean, empty flask, and then the system pressure was increased to 2,500 psig (17.24 MPa).

6. The system pressure was maintained at 2,500 psig (17.24 MPa) until no other solid material was observed eluting from the system. 173.39 g of grayish white solids were collected and marked as 'Fraction 2'.

7. The fraction 2 sample collected at 2,500 psig (17.24 MPa) was then allowed to degas at room temperature and pressure for at least two days before being characterized using the test methods described herein.

Data for the fraction 2 sample collected at 2,500 psig (17.24 MPa) are summarized in Table 2.

The solids isolated in fraction 2 in this example were gray to off-white in color. When the solids from fraction 2 were compression molded into square test specimens, the specimens were cream/light gray in color. A photograph of the square test specimen is shown in Fig. 4 as Example 7. As shown in Fig. 4, the sample improved slightly with respect to Example 1. Even without the solid medium contact step, the values deL*a*b*show that the square test specimens of fraction 2 of Example 7 improved somewhat in terms of color with respect to the samples of Example 1 (i.e., post-consumer polypropylene as received) . The L*values for the square test specimens of fraction 2 of Example 7 averaged 50.51, somewhat improved compared to the L*values of the square test specimens of Example 1, which averaged 39.76. . The opacities of the square test specimens of fraction 2 of Example 7, which had an average opacity of 87.20%, also improved somewhat compared to the opacity values of the square test specimens of Example 1, which had an average opacity of 87.20%. average opacity of 100%. Although not intended to impose any theory, the slight improvement in the color values and opacities of the square test specimens of Example 7 may be due to the extraction of the polymer from the dyes and other materials responsible for the appearance. Furthermore, the applicants believe that dyes and other materials may remain as residue after the polymer is extracted.

The concentration of heavy metal contamination for the fraction 2 samples of Example 7 improved compared to the samples of Example 1. For example, the sodium concentration in the fraction 2 samples of Example 7 averaged 33,300 ppb while the sodium concentration in the samples of Example 1 averaged 136,000 ppb (a reduction of approximately 76%). The concentrations of aluminum, calcium, titanium, chromium, iron, nickel, copper, zinc, cadmium and lead were reduced by more than 69% for the samples of fraction 2 of Example 7 with respect to the samples of Example 1. Although without To impose any theory, the applicants believe that the reduction in heavy metal contamination results from extracting the polymer away from the contamination, which remains as residue after extracting the polymer.

The samples of fraction 2 of Example 7 had an average ash content value of approximately 0.3154% by weight, which was lower than the ash content values corresponding to the samples of Example 1, which had an average of approximately 1.2117% by weight.

The samples of fraction 2 of Example 7 were found to have an odor intensity of 1 on a 5-point scale (5 being the most intense), which was much better compared to the odor intensity of the samples of Example 1 , which had an odor intensity of 3.75. Samples from fraction 2 of Example 7 had an odor described as “plastic-like” or “petroleum-like.”

The samples of fraction 2 of Example 7 had an average polyethylene content value of approximately 1.2% by weight, which improved compared to the polyethylene content of the samples of Example 1, which had an average of approximately 5 .5% by weight.

Example 8

The post-consumer polypropylene mixed color flake sample described in Example 1 was purified using a procedure based on the procedure described in EP0849312 A1.

20.00 g of post-consumer recycled polypropylene mixed color flakes were combined with 400.04 g of mineral spirits (Sigma-Aldrich, USA) in a 1 L round bottom flask. . The mixture was kept at room temperature for 22 hours with occasional stirring. The mineral spirits were then decanted from the polymer. 402.60 g of fresh mineral spirits were added to the flask containing the polymer. The mixture was then heated and kept at 140 °C for 90 min under reflux. The resulting hot solution was vacuum filtered through a 70 mm ID Buchner funnel with a layer of glass wool as a filtration medium. Approximately 300 ml of filtrate was collected and allowed to cool to room temperature. The resulting gray precipitate was isolated by vacuum filtration through a 70 mm ID Buckner funnel with sharkskin filter paper. The gray precipitate was combined with 2.01 g of Fuller's earth (Sigma-Aldrich, USA) and 195.21 g of fresh mineral spirits in a 1 L round bottom flask and then heated and maintained at 140 °C for 30 min at reflux. The resulting hot solution was vacuum filtered through a 5.5 cm ID Buchner funnel with sharkskin filter paper. The filtrate was allowed to cool to room temperature. The resulting light gray precipitate was isolated by vacuum filtration through a 5.5 cm ID Buchner funnel with sharkskin filter paper. The isolated precipitate was dried in a vacuum oven at 25 °C for approximately 18 hours. Approximately 4.82 g of dry precipitate were isolated. The isolated precipitate was then extracted with acetone for 30 min using a Soxhlet extraction apparatus fitted with a cellulose extraction cartridge. The extracted material was dried in a vacuum oven at 25 °C for approximately 19 hours. 3.4654 g of material were recovered. The sample was characterized using the test method described herein and the resulting data is summarized in Table 2.

The isolated solids in this example were light gray to off-white in color. When these solids were compression molded into square test specimens, the specimens had a grayish smoky appearance. A photograph of the square test specimen is shown in Fig. 4 as Example 8. As shown in Fig. 4, the specimen improved but remained dark in color nor was it as transparent and translucent as virgin PP. The L*a*b*values showed that the color of the sample was improved compared to the samples of Example 1 (i.e., post-consumer recycled polypropylene as received). The L*values for the sample from Example 8 was 63.15, which was an improvement compared to the L*values for the sample from Example 1, which averaged 39.76. However, the L* value of the sample from Example 8 demonstrates that the method described in EP0849312 A1 does not produce a sample that is as bright and colorless as samples from some of the embodiments of the present invention. The opacity of the Example 8 sample was 24.96% opacity, which was an improvement compared to the opacity values of the Example 1 samples, which averaged 100% opacity. The opacity value also shows that the sample of Example 8 was not as translucent as some of the embodiments of the present invention.

The concentration of heavy metal contamination of the sample of Example 8 was improved compared to the samples of Example 1. For example, the sodium concentration in the sample of Example 8 was 5,120 ppb while the sodium concentration in the samples of Example 8 was 5,120 ppb. Example 1 averaged 136,000 ppb (a reduction of approximately 96%). The concentrations of aluminum, calcium, titanium, chromium, iron, nickel, copper, zinc, cadmium and lead were reduced by more than 43% for the sample of Example 8 relative to the samples of Example 1.

The sample of Example 8 had an ash content of approximately 0.3294% by weight, which was lower than the ash content values in the samples of Example 1, which averaged approximately 1.2117% by weight.

The samples of Example 8 had an odor intensity of 5 on a 5-point scale (5 being the most intense), which was much more intense compared to the odor intensity of the samples of Example 1, which had an intensity of smell of 3.75. The samples of Example 3 had an odor described as “gasoline-like.” The strong odor of this sample was due to the residue of the turpentine solvent used.

The sample of Example 8 had average polyethylene content values of approximately 5.5% by weight, which was the same as the average polyethylene content in the samples of Example 1, of approximately 5.5% by weight.

Comparative Virgin Polypropylene Samples

Pro-fax 6331 polypropylene (LyondellBasell Industries Holdings, B.V.) was used for all “virgin PP” comparative samples. The virgin PP granules were processed into square test specimens according to the method described herein. The L*a*b*values for the specimens made from virgin PP had an average of 85.13 ± 0.18, -0.71 ± 0.01 and 2.27 ± 0.02, respectively. The square test specimens had an average opacity of 7.56 ±0.21%. The virgin PP beads had an odor intensity of 0.5 on a 5-point scale (5 being the most intense) and had an odor described as “plastic.”

Example 9

A sample of post-consumer recycled high-density polyethylene was obtained from a recycled resin supplier. The post-consumer recycled polyethylene was classified as “natural colour” and came from the United Kingdom. The received granules were characterized using the test methods described herein and the resulting data are summarized in Table 3. The purpose of this example is to show the properties of a representative post-consumer recycled polyethylene resin before purification according to an embodiment of the present invention.

The granules and the corresponding square test specimens were cream colored as indicated by the L*a*b* values of the square test specimens. The opacity of the sample from Example 9 was approximately 81.61% opaque. A photograph of the square test specimen is shown in Fig. 6 as Example 9.

This example serves as a representative basis of heavy metal contamination present in recycled polyethylene obtained after consumption. Compared to the other example, heavy metal contamination was found to be higher in post-consumer recycled polyethylene.

The samples of Example 9 had ash content values averaging approximately 0.8513% by weight, which also serves as a basis for the amount of non-combustible substances that may be present in the recycled polyethylene obtained post-consumer. .

This example also serves as a representative basis of contamination by odorous compounds present in recycled polyethylene obtained after consumption. The samples of Example 9 were found to have an odor intensity of 2.5 on a 5-point scale (5 being the highest intensity).

Example 10

The post-consumer recycled polyethylene sample described in Example 9 was processed using the experimental apparatus shown in Fig. 3 and the following procedure:

1. 237 g of polyethylene granules were loaded into the pressurized vessel of a 1.1 L extraction column with an internal diameter (ID) of 1.75" (44.45 mm) and a length of 28" (71 .12 cm) that was heated to an external surface temperature of 175 °C.

2. The liquid n-butane solvent was pressurized to approximately 4500 psig (31.03 MPa) using a positive displacement pump and preheated to a temperature of approximately 110 °C using two heat exchangers before being introduced into the bottom of the extraction column.

3. The fluid stream leaving the top of the extraction column was introduced into the top of a second 0.5 L pressure vessel with an ID of 2" (50.8 mm) and a length of approximately 8.5" (21.59 cm) that was heated to an external surface temperature of 175°C. The second pressurized container contained 150 ml of silica gel (Silicycle Ultra Pure Silica Gels, SiliaFlash GE60, Parc-Technologies, USA) previously mixed in a beaker with 150 ml of aluminum oxide (Activated Alumina). , Selexsorb CDX, 7x14, BASF, USA).

4. The fluid stream exiting the bottom of the second pressure vessel was depressurized through an expansion valve into a side-arm Erlenmeyer flask. After depressurizing the fluid stream into the Erlenmeyer flask, the solvent vapor was purged through the side arm opening hole and the liquids/solids were collected in the flask. The n-butane solvent was eluted through the system at 4500 psig (31.03 MPa) until no additional material was observed accumulating in the flask. 3.93 g of white solids were collected and marked as 'Fraction 1'.

5. The Erlenmeyer flask was replaced with a clean, empty flask, and then the system pressure was increased to 5000 psig (34.47 MPa).

6. The system pressure was maintained at 5000 psig (34.47 MPa) until no other solid material was observed eluting from the system. 33.19 g of white solids were collected and marked as 'Fraction 2'.

Data for fraction 2 samples collected at 5,000 psig (34.47 MPa) are summarized in Table 3.

The fraction 2 solids isolated in this example were white to off-white in color. When the fraction 2 solids were compression molded into square test specimens, the specimens were cream colored. A photograph of the square test specimen is shown in Fig. 3 as Example 10. As shown in Fig. 6, the specimen was more translucent than untreated PE and had an opacity similar to that of virgin polyethylene. The L*a*b* values also show that the square test specimens of fraction 2 of Example 10 showed an improvement in color with respect to the samples of Example 1 (i.e., polyethylene obtained after consumption as as received). The L*values for the square test specimens of fraction 2 of Example 10 averaged 85.20, improved compared to the L*values of the samples of Example 9, which averaged 80.28. The opacity of the square test specimens of fraction 2 of Example 10, which had an average opacity of 53.20%, was also improved compared to the opacity values of the samples of Example 9, which had an average opacity of 81.61%.

The concentration of heavy metal contamination for the fraction 2 samples of Example 10 also improved compared to the samples of Example 9. For example, the sodium concentration in the fraction 2 samples of Example 10 averaged 6.620 ppb while the sodium concentration in the samples of Example 9 averaged 19,800 ppb (a reduction of approximately 67%). All concentrations of all other elements measured were reduced by more than 66% for the fraction 2 samples of Example 10 relative to the samples of Example 9.

The fraction 2 samples of Example 10 had an average ash content value of approximately 0.5032 wt%, which was lower than the ash content values for the samples of Example 9, which had an average of approximately 0.8513% by weight.

The samples of fraction 2 of Example 10 were found to have an odor intensity of 0.5 on a 5-point scale (5 being the most intense), which was better compared to the odor intensity of the samples of Example 9, which had an odor intensity of 2.5.

Fig. 7 is a bar graph of the opacity and odor intensity of purified recycled polyethylene from Example 10 compared to untreated recycled polyethylene (Example 9) and a comparative sample of virgin polyethylene. As shown in Fig. 7, the purified recycled polyethylene of Example 10 had improved opacity and odor intensity.

Table 3. Removal of color, contamination and odor from Examples 9 and 10

_________ _________

Comparative samples of virgin polyethylene

Dow 6850A polyethylene (The Dow Chemical Company, USA) was used for all “virgin PE” comparative samples. The virgin PE granules were processed into square test specimens according to the methods described herein. The L*a*b*values for the specimens made from virgin PE averaged 84.51 ± 0.97, -1.03 ± 0.04, and -0.63 ± 0.12, respectively. The square test specimens had an average opacity of 34.68 ±0.69%. The virgin PE beads had an odor intensity of 0.5 on a 5-point scale (5 being the most intense) and had an odor described as “plastic.”

Claims (12)

i. A method for purifying regenerated polymers, wherein the regenerated polymers are polyolefins, the method comprising: to. Obtaining a regenerated polymer wherein said regenerated polymer is selected from the group consisting of post-consumer use polymers, post-industrial use polymers, and combinations thereof; b. Contacting the regenerated polymer at a temperature of 80°C to 220°C and a pressure of 150 psig (1.03 MPa) to 15,000 psig (103.42 MPa) with a first fluid solvent to produce an extracted regenerated polymer, wherein the polymer is practically insoluble in the fluid solvent; c. Dissolve the extracted regenerated polymer in a solvent selected from the group consisting of the first fluid solvent, a second fluid solvent, and mixtures thereof, at a temperature of 90°C to 220°C, and at a pressure of 350 psig (2 .41 MPa) to 20,000 psig (137.90 MPa) to produce a polymer solution, wherein the fluid solvents have a standard boiling point less than 70 °C; d. Purifying said polymer solution at a temperature of 90 ° C to about 220 ° C and at a pressure of 350 psig (2.41 MPa) to 20,000 psig (137.90 MPa) by contacting said polymer solution with solid media to produce a purer polymer solution, wherein the solid media is selected from the group consisting of inorganic substances, carbon-based substances or mixtures thereof or wherein the solid media is recycled glass; and wherein the inorganic substances are selected from the group consisting of silicon oxides, aluminum oxides, iron oxides, aluminum silicates, magnesium silicates, amorphous volcanic glasses, silica, silica gel, diatomite, sand, quartz, glass regenerated, alumina, perlite, fuller's earth, bentonite and mixtures thereof, and the carbon-based substances are selected from the group consisting of anthracite coal, carbon black, coke, activated carbon, cellulose and mixtures thereof ; and and. Separating a purer polymer from said purer polymer solution; wherein said second fluid solvent has the same chemical composition or a different chemical composition as the first fluid solvent. 2. The method of claim 1, wherein the purer polymer is separated from said purer polymer solution at a temperature of 0 ° C to 220 ° C and at a pressure of 0 psig (0 MPa) to 2,000 psig (13 .79 MPa). 3. The method of any of the preceding claims, wherein the regenerated polymer is recycled polymer obtained after consumption. 4. The method of any of the preceding claims, wherein said fluid solvent has a standard boiling point of less than 0°C and greater than -45°C and a standard enthalpy change of vaporization of less than 25 kJ/mol. 5. The method of any of the preceding claims, wherein said fluid solvent is selected from the group consisting of olefinic hydrocarbons, aliphatic hydrocarbons and mixtures thereof. 6. The method of any of the preceding claims, wherein said fluid solvent is n-butane, butane isomers, or mixtures thereof. 7. The method of any of the preceding claims, wherein said temperature in steps b, c and d is from 110 °C to 170 °C. 8. The method of any of the preceding claims, wherein said pressure in step b is 1,100 psig (7.58 MPa) to 5,500 psig (37.92 MPa). 9. The method of any of the preceding claims, wherein said pressure in step b is less than 1,100 psig (7.58 MPa). 10. The method of any of the preceding claims, wherein said pressure in step c is greater than 1,100 psig (7.58 MPa). 11. The method of any of the preceding claims, wherein said contacting of the polymer solution with said solid medium is carried out in a compacted bed of said solid media. 12. The method of claim 11, wherein said packed bed has a length greater than 20 cm.